Molecular Switches
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H |
O |
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N |
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O |
H |
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n N |
N |
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N |
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H |
N |
N |
n |
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CO2H |
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H |
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CO2H
(16a) |
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hν |
∆ |
H O |
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N |
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n N |
N |
H |
N |
CO2H |
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(16b)
O |
N |
H
CO2H n
P M
M
A
A
A 
X
B
S
S
hν1
hν2
B
P
B
Enzyme inactive-"OFF" |
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Enzyme active-"ON" |
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x |
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H3C |
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y |
370nm > λ > 330nm |
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x |
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H3C |
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y |
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C O |
C O |
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λ > 400nm |
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C O |
C O |
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NH2 |
NH |
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NH2 |
NH |
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N |
N
N
N
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(17a) |
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(17b) |
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x |
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H3C |
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y |
400nm > λ > 360nm |
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x |
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H3C |
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y |
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C O |
C O |
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λ > 475nm |
C O |
C O |
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NH2 |
O |
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NH2 |
O |
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(CH2)2 |
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(CH2)2 |
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O2N |
O N |
O2N |
N |
+ |
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(18a) |
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O– |
(18b) |
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H3C |
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uv |
H3C |
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x |
y |
x |
y |
C O |
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C O |
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NH2 |
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NH2 |
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(H3C)2N |
C |
N(CH3)2 |
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OH |
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(H3C)2N |
C |
N(CH3)2 |
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+ |
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OH– |
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(19a) |
(19b) |
P M
F V F V
O 
NO2
N |
H2O |
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H |
HN |
O |
CO2H
(20)
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O |
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OH |
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HN |
O |
NO2 |
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+ |
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CO2H |
H2N |
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(21)
(A)
[para-nitroaniline] ( M)
(B)
[para-nitroaniline] ( M)
22
(d)
16
(b)
10
4 |
(c) |
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(a) |
–2
0 |
2.5 |
5 |
7.5 |
10 |
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time (min) |
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20
13
(b) + (d)
6
(a)
(c)
0 
0 |
200 |
400 |
600 |
time (sec)
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P M
F V F V
P M
F V
F V
A)
B)
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S |
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S |
Electrical |
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B |
Output |
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R+ |
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R |
+ |
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P |
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P |
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hν1 |
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hν2 |
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B |
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e- R |
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e |
- R |
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Redox Center |
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Electrical |
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S |
Output |
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Protein |
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hν1 |
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B |
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e |
- |
hν2 |
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P |
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e- |
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Redox Center |
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F V
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e- |
CO2H |
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Fe |
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SP |
SP |
SP |
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O |
SP |
(23) |
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Glucose |
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O |
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O |
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S CH2CH2 C O N |
S CH2CH2 |
C O N Lys |
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O |
Lys |
H |
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(22a) |
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CO2H |
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Gluconic |
Switch-ON |
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Fe + |
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Acid |
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O |
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SP |
= |
C |
N |
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O |
λ> 475nm 320nm< λ <380nm
-H+ +H+
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e- |
CO2H |
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Fe |
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NO2 |
MRH + |
MRH |
+ |
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(23) |
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O |
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Glucose |
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+ |
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O |
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MRH + |
= |
C |
S CH2CH2 |
C O N Lys |
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N |
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H |
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(22b)
HO |
CO2H |
Switch-OFF |
Fe + |
Gluconic |
NO2 |
Acid |
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80 |
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70 |
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(a) |
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60 |
A |
60 |
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/ |
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cat |
50 |
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A |
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I |
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40 |
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(b) |
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/ |
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40 |
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I |
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1 |
2 |
3 |
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Cycle number |
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20 |
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0 |
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–0.2 0 0.2 0.4 0.6
E / V
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0 M |
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0 M |
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M M |
F V
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F V
F V
F V
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200 |
120 |
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/ nA |
80 |
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(b) |
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I |
40 |
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/ nA |
100 |
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0 |
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MRH |
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MRH |
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MRH |
SP |
SP |
SP |
(a) |
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I |
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+ |
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+ |
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+ |
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0 |
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0 |
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0.2 |
0.4 |
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E / V |
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0 M |
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0 M |
M |
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M |
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F V
F V
F V F V
F
V
F V